Nonionic surfactants



United States Patent 3,322,790 NONIONIC SURFACTANTS Henry E. Fritz,Charleston, and Harry T. Zika and Edmund C. Steinle, Jr., SouthCharleston, W. Va., assignors to Union Carbide Corporation, acorporation of New York No Drawing. Filed Nov. 1, 1962, Ser. No. 234,8359 Claims. (Cl. 260-3321) This invention relates to a novel class ofnonionic surfactants. More particularly, this invention relates tomodified nonionic surfactants containing a sulfone-containing groupwhich are characterized by reduced foam-forming tendencies. In anotheraspect, this invention relates to nonionic surfactants having lowercloud points than previously known nonionic surfactants and which aresuitable for use as cold-water detergents.

Nonionic surface active agents or surfactants are well known to berelatively high molecular weight compounds consisting of a hydrophobicportion to which is attached a solubilizing group or hydrophilicelement, containing groups such as ether links (-O), hydroxyl groups(-'OH), carbonyloxy groups 0 ll carbamyl groups 0 (&NH) and the like.With very few exceptions, the nonionic surfactants contain at least onehydroxyl group. These nonionic, hydroxyl-containing surfactants arewidely employed as emulsifiers, wetting agents, penetrants, dyeassistants, detergents and the like. Many of the nonionic,hydroxyl-containing surfactants exhibit a tendency to produce high,stable foams when in aqueous mixtures which are subject to agitation.This foam-forming tendency is often undesirable, particularly when thesurfactant is employed as a laundry detergent. The foam cushions theagitation of the laundry in the modern automatic washing machines,thereby reducing the cleaning efficiency of the detergent.

It has now been found by this invention, however, that when thenonionic, hydroxyl-containing surfactant is reacted with an olefinicallyunsaturated sulfone, as hereinafter defined, the resulting compound hasless tendency to form high, stable foams than the hydroxyl-containingsurfactant, while retaining the ability to reduce surface tension anddetergent properties of the hydroxyl-containing surfactant. In addition,the compounds of this invention have lower cloud points (the temperatureat which an aqueous solution of the surfactant becomes cloudy onincreasing the temperature of the solution). Thus, the nonionicsurfactants of this invention are useful as cold water detergents, andcan be employed at temperatures at or slightly above room temperature.In addition to their outstanding utility as laundry detergents, thecompounds of this invention can be employed as emulsifiers, wettingagents, penetrants, dye assistants and the like.

The nonionic, surface active agents of this invention generally consistof the residue of a nonionic, hydroxyl containing, surface activecompound bonded at the site of a hydroxyl group through the oxygen atomof said hydroxyl group to a fi-hydrocarbylmonosulfone group. Thesecompounds are represented by the general formula:

(I) zrE-( m. wherein Z is the residue of an organic, nonionic,hydroxylcontaining, surface active compound containing n bydroxylgroups; E is a ,B-hydrocarbylmonosulfone group containing from 3 to 14carbon atoms having a valence 3,322,790 Patented May 30, 1967 of m+1wherein the valence bonds are from carbon atoms; m is an integer havinga value of from 0 to l; and n is an integer having a value of at least1, preferably from 1 to about 4, and is 1 when m has a value of 1.

By the phrase residue of an organic, nonionic, hydroxyl-containingsurface active compound containing n hydroxyl groups, as employed in thespecification and appended claims, is meant that portion of thewell-known hydroxyl-containing, nonionic, surface active compoundscontaining 12 hydroxyl groups, which remains after removal of a hydrogenatom from a hydroxyl group, and may be considered as being an organicradical having a valence of 11 whose valence bonds are from oxygen atomsbonded to carbon atoms.

By the phrase ";3-hydrocarbylmonosulfone group having a valence of m+lis meant a monovalent or divalent group consisting soley of hydrogen,carbon and the divalent sulfonyl group (SO wherein the sulfonyl group isbonded to two different carbon atoms and wherein the valence bonds arefrom a carbon atom 3- to the sulfonyl group. In general, thefi-hydrocarbylmonosulfone groups are represented by the formula:

wherein R when taken alone, is a divalent alkylene group containing from2 to 10, preferably from 2 to 4, carbon atoms wherein one valence bondit attached to the sulfonyl group, and the second valence bond is froman aliphatic carbon atom which is {3- the sulfonyl group as ethylene,propylene, 1,2-butylene, 2,3-butylene, 1,2-hexylene, 2,3-hex-ylene,3,4-hexylene, 1,2-octylene, 2,3-octylene, 3,4-octylene, 4,5-octylene andthe like; R when taken alone, is either R or an alkyl group containingfrom 1 to about 10, preferably from 1 to 4, carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, tert.- butyl, iso-butyl,iso-pentyl, octyl, dodecyl, and the like, and R and R when takentogether, form a trivalent saturated hydrocarbon chain containing from 3to 14 carbon atoms, each of whose valence bonds is from a differentcarbon atom, two of such bonds being separated by at least 3 carbonatoms and being attached to the sulfonyl group, to form a cyclic ringhaving from 4 to 7 ring members, the third bond being from a carbon atom,8- the sulfonyl group. As is apparent from the foregoing discussion,the hydrocarbylmonosulfone group can be in the form of a monovalent ordivalent open chain structure or a monovalent heterocyclic structurecontaining the sulfonyl group. As examples of monovalent, open chainhydrocarbylmonosulfone groups one can mention 2-(methylsulfonyl)ethyl,2-(ethylsulfonyl)ethyl, 2-propylsulfony1)ethyl,2-(iso-propylsulfonyl)ethyl, Z-(n-butylsulfonyl)ethyl,2-(isobutylsulfonyl)ethyl, 2-(tert.-butylsulfonyl)ethyl, 2(octylsulfonyl)ethyl, 2 (dodecylsulfonyl)ethyl,2-(methylsulfonyl)propyl, and the like. As examples of divalent,open-chain, hydrocarbylmonosulfone groups one can mentionbis(dimethylene)sulfone, ethylene propylene sulfone, dipropylenesulfone, and the like. As examples of monovalent, heterocyclichydrocarbylmonosulfone groups one can mention 3 -thiethy-1,1-dioxide,

2-methyl-3 -thietiyl-1,1-dioxide,

3 -methyl-3 -thietyl-1,1-dioxide,

2,3 ,4-trimethyl-3 -thietyl-1,1-dioxide, 2-ethyl-3-thietyl-1,l-dioxide,

2-propyl-3 -thiety-1,1-dioxide, 2-butyl-3-thietyll 1 -dioxide,

3 -tetrahydrothiophyl-1,1-dioxide, 2-methyl-3-tetrahydrothiophyl-1,1-dioxide, 3 -methyl-3-tetrahydrothiophenyl-1,l-dioxide, 4-methyl-3 -tetrahydrothiophyl-1, l-dioxide, 5-methyl-3-tetrahydrothiophyl-1,1-dioxide,

Subgeneric to the compounds of Formula I are the compounds of thefollowing formulae:

wherein Z, n and R are as defined above; R is an alkyl group containingfrom 1 to about 10 carbon atoms; and a R is a trivalent, saturatedhydrocarbon chain containing from 3 to 14 carbon atoms, each of whosevalence bonds is from a different carbon atom, two of such bonds beingseparated by at least 3 carbon atoms and being attached to the sulfonylgroup to form a cyclic ring having from 4 to 7 ring members, the thirdbond being from a carbon atom the sulfonyl group.

Preferred fl-hydrocarbylmonosulfone groups are the 3-tetrahydrothiophyl-1,1-dioxide groups of the formula:

wherein each R is either hydrogen or alkyl of from 1 to about 4 carbonatoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl andtert.-butyl. In addition, 3- tetrahydrothiophyl-l,l-dioxide groupswherein each R can be an alkoxy group of from 1 to 4 carbon atoms suchas methoxy, ethoxy, propoxy and butoxy, or alkanoyloxy of from 2 to 4carbon atoms such as acetoxy, propionoxy or butyroxy, can be employedand are fully equivalent to the B-hydrocarbylmonosulfonyl groups for thepurposes of this invention.

As indicated above, the compounds of this invention are produced by thebase-catalyzed reaction of a nonionic, hydroxyl-containing, surfaceactive agent with an olefinically unsaturated sulfone. In this reaction,the hydroxyl group reacts with the olefinic double bond to produce anether group, as illustrated by the reaction of a nonionichydroxyl-containing surfactant with 2,5-dihydrothiophene-l,l-dioxide.

O O 0 On wherein Z and n are as defined above.

The nonionic, hydroxyl-containing surfactants employed in this reactionare well known compounds, and can be considered as consisting of ahydrophobic moiety chemically bonded to a hydrophilic moiety. Ingeneral, the hydrophobic moiety is the residue of an organic,hydrophobic compound containing at least one active hydrogen atom andthe hydrophilic moiety is a saturated organic chain containingsolubilizing groups such as ether oxygen, hydroxyl groups, carbonyloxygroups, carbamyl groups and the like, and containing at least onehydroxyl group. The hydrophilic moiety is bonded to the residue of thehydrophobic moiety at the site on the hydrophobic moiety occupied bysaid active hydrogen atom.

Although the ,B-hydrocarbylmonosulfone group present on the compounds ofthis invention is not employed for the purpose of additionalhydrophilicity, it can be considered as composing a portion of thehydrophilic moiety of the compounds of this invention. Thus, thecompounds of this invention can be further considered as consisting of ahydrophobic moiety chemically bonded to a hydrophilic moiety, whereinthe hydrophobic moiety is the residue of an organic hydrophobic compoundcontaining at least one active hydrogen atom, said hydrophobic moietybeing bonded at the site of said active hydrogen atom to a hydrophilicmoiety consisting of the residue of a hydroxylcontaining hydrophilicchain bonded through the oxygen atom of a hydroxyl group to aB-hydrocarbylmonosulfone group.

The nonionic, hydroxyl-containing surfactants employed in producing thecompounds of this invention can be classified generally according to thestructure of the hydrophilic moiety of the compound. The great bulk ofthese surfactants have as the hydrophilic moiety one or more chainscontaining one or more alkyleneoxy groups, and have the general formulawherein Y is the residue of an organic hydrophobic compound containing yactive hydrogen atoms; y is an integer having a value of at least 1,generally from 1 to about 6 and preferably from 1 to about 4; X is analkyleneoxy chain; and H is a hydrogen atom bonded to an oxygen atom ofsaid alkyleneoxy chain.

By the term residue of an organic hydrophobic compound containing yactive hydrogen atoms is meant that portion of a hydrophobic compoundhaving y active hydrogen atoms which remains after the active hydrogenatoms have been removed, and thus, is an organic radical, or group ofatoms, having a valence of y.

By the term alkyleneoxy chain, as employed in the specification andclaims, is meant a chain containing one or more alkyleneoxy groups. Bythe term alkyleneoxy group as employed in the specification and claims,is meant a divalent alkylene group, such as methylene, ethylene,propylene, butylene, styrene (CH CH(C H and the like; bonded to anoxygen atom in a manner such that one of the valences of the alkyleneoxygroup is from an oxygen atom and the other is from a carbon atom. Asexamples of alkyleneoxy groups one can mention methyleneoxy (CH O),ethyleneoxy (C H O-), propyleneoxy, (-C H O-), butyleneoxy (C H O),styreneoxy (-C H '(C H )O-) and the like.

By the term active hydrogen atom is meant a hydrogen atomwhich reactswith methyl magnesium iodide to produce methane in the well-knownZerewitinoff reaction (Niederl and Niederl, Micromethods of QuantitativeOrganic Analysis, p. 263, John Wiley & Sons, New York city, 1949).Active hydrogen atoms of this type are normally members of a functionalgroup containing an oxy-- gen atom, for example, hydroxyl, whetherbonded to an aliphatic or aromatic carbon, a carboxyl group, aphosphinico group P(O) OH), and the like; a nitrogen atom,

such as amino, imino, amido, hydrazino, hydrazo, guanido, guanyl,sulfonamido, ureido, thioureido and the like; or a sulfur atom, such asmercapto, thiocarboxyl, and the like. In addition, a hydrogen atom maybe activated by proximity to a carbonyl group, as in cyanoactic esters,acetoacetic esters, malonic esters and the. like.

As examples of suitable hydrophobic active-hydrogencontaining compoundswhich can be employed in producing the nonionic surfactants of the typerepresented by the Formula VI one can mention:

(1) Saturated and unsaturated aliphatic and cycloaliphatic carboxylicacids, particularly those acids having from about 7 to about 25 carbonatoms, such as enanthic acid, eaprylic acid, capric acid, hendecanoicacid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleicacid,

linolenic acid, eleostearic acid, abietic acid and the like. (2) Dialkylesters of phosphoric acid of the formula wherein each R is alkyl of from6 to 12 carbon atoms, such as bis(hexoxy)phosphonic acid,bis(2-ethylhexoxy)- phosphonic acid, bis (dodecoxy) phosphoric acid, andthe like.

(3) Alkylated phenols, particularly those containing from about 4 toabout 22 carbon atoms in the alkyl group thereof, for example,butylphenol, amylphenol, hexylphenol, octylphenol, nonylphenol,dodecylphenol, nonadecylphenol, and the like. These compounds arenormally the para-isomer, although some ortho-isomers may be present inthe commercially obtainable product. In addition, one can employ complexphenols, such as those obtained by the condensation of phenol with analdehyde or a ketone. An example of this type of compound is thecondensation product of alkylcyclohexanone and phenol having theformula:

(4) Aliphatic and cycloaliphatic alcohols containing from about 8 toabout 22 carbon atoms, such as octyl alcohol, nonyl alcohol, decylalcohol, coco alcohol (a mixture of C to C alcohols), lauryl alcohol,oleyl alco hol, tallow alcohol (a mixture of C to C alcohols), cetylalcohol, stearyl alcohol, hydroabietyl alcohol, tridecyl alcohol,2,6,8-trimethyl-4-nonyl alcohol, eicosanyl alcohol linoleyl alcohol,octylcyclohexanol, 9-phenylstearyl alcohol, lO-phenylstearyl alcohol andthe like. Polyhydric alcohols can also be employed, for example sorbitolglucosides of alkylphenols or mono fatty acid esters ofanhydrosorbitols, fatty acid derivatives of trimethylolaminomethane ofthe formula CHZOH RCNH-C CHzOH CHzOH the reaction product of stearichydroxide and glycidol of the formula (I) (IJH OH RC ONHNH-CH CHzOH andthe like.

(5) Alkyl mercaptans having from about 8 to about 22 carbon atoms, suchoctyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan,eicosyl mercapstan and the like.

(6) Fatty acid amides having from 5 to about 20 carbon atoms, such ascapramide, lauramide, coconut oil amides, oleamide, myristamide,stearamide and the like.

(7) Hydrophobic alkylene-oxide polymers consisting of the residue of anorganic compound containing at least one active hydrogen atom,preferably from 1 to about 6 active hydrogen atoms, bonded at the sideof said active hydrogen atom to an alkyleneoxy chain having an atomicratio of carbon to oxygen of at least 2.75, generally from 2.75 to about8, and preferably from 3 to about 4. The alkyleneoxy chains usuallycontain propyleneoxy units, either alone or in combination withethyleneoxy units or butyleneoxy units, although styreneoxy units havealso been employed. The specific composition of these hydrophobicalkylene oxide polymers will vary widely depending upon the nature ofthe residue of the active hydrogen-containing compound, i.e., whether itis hydrophilic or hydrophobic, and the nature of the alkyleneoxy group.In general, the more carbon atoms present in the alkyleneoxy group, thefewer alkyleneoxy groups are necessary in an alkyleneoxy chain toproduce a hydrophobic polymer. For example, to be hydrophobic, a polymerproduced by the reaction of butanol with propylene oxide must have anaverage molecular weight of at least about 450, whereas a polymerproduced by the reaction of butanol and butylene oxide is hydrophobic ata molecular weight of only 350. As examples of suitable activehydrogen-containing compounds one can mention methanol, butanol, formicacid, acetic acid, butanoic acid, diethyl amine, ethyl butylamine,methyl acetamide, methyl mercaptan, butyl mercaptan, N-propylethanesulfonamide, ethylene glycol, 1,3-butylene glycol,1.5-pentanediol, sucrose, glycerine, resorcinol, oxalic acid, glycolicacid, acetamide, benzene sulfonamide, ethanolamine, diethanolamine,triethanolamine, butyl-amine, aniline, ethylene diamine, diethylmalonate and the like.

The hydrophilic alkyleneoxy chain represented by -X- in Formula VIabove, is generally an ethyleneoxy chain, or a chain composed of amixture of ethyleneoxy units and either methyleneoxy units orpropyleneoxy units, wherein the atomic ratio of carbon to oxygen is fromabout 1.5 :1 to about 2.111. The ethyleneoxy units are employed forhydrophilicity, and the methyleneoxy and propyleneoxy units, althoughnot hydrophilic in nature, are employed to modify the character of thehydrophilic alkyleneoxy chain. The length of the alkyleneoxy chain willvary depending upon the nature of the hydrophobic moiety and theproperties desired in the resultant surfactant. In general, greaterwater solubility is obtained as the number of ethyleneoxy unitsincreases. When the hydrophilic moiety is a poly(ethyleneoxy) chain, themost useful products are obtained when the molecular weight of thepoly(ethyleneoxy) chain is from about 25 to about 900 percent of themolecular weight of the hydrophobic moiety.

The surface active compounds of Formula VI can be further classifiedaccording to the number of alkyleneoxy groups in the alkyleneoxy chain;i.e., Whether the alkyleneoxy chain contains only one alkyleneoxy groupor whether it is a poly(alkyleneoxy) chain.

The surfactants having only one alkyleneoxy group in the alkyleneoxychain are exemplified by the alkanolamide condensates, produced by thereaction of a fatty acid with diethanolamine.

The surfactants having poly(alkyleneoxy) chains are generally producedby the reaction of an active hydrogencontaining hydrophobe with ethyleneoxide, wherein the alkyleneoxy chain consists of a series of ethyleneoxygroups (-C H O), usually from about 4 to about 50 ethyleneoxy groups.Heteric poly(methyleneoxy)-poly- (ethyleneoxy) chains can be produced,for example, by the reaction of an active hydrogen containinghydrophobic compound with formaldehyde and either ethylene glycol orethylene oxide, and the heteric poly(ethyleneoxy)-poly- (propyleneoxy)chains can be produced by the reaction of an active-hydrogen-containing,hydrophobic compound with a mixture of ethylene oxide and propyleneoxide. Poly(ethyleneoxy) chains can also be formed from polyethyleneglycols by the reaction of the active-hydrogencontaining hydrophobe withthe glycol.

The second broad class of hydroxyl-containing nonionic surfactants arepartial ethers or partial esters of polyhydric alcohols other thanethylene glycol or polyethylene glycol. As examples of compounds of thistype one can mention (1) Fatty acid partial esters of sorbitans(anhydrosorbitols), such asZ-(hydroxymethyl)3,4,5-trihydroxytetrahydropyran, 2- 1',2'-dihydroxyethyl) -3,4-dihydroxytetra- CHzCHaOH hydrofuran,3,6-dihydroxyhcxahydrofuro[3,2-b]furan and the like.

(2) Low molecular Weight alkylmethylolphenol esters of glucose orsorbital. For example, amylor hexylphenol, when hydroxymethylated andreacted with sorbitol, gives a somewhat water soluble compound of theformula l CHzOCHflCHOHMCIIgOII (3) Glucosides of hydrophobic alcoholsand phenols.

(4) Reaction products of a fatty acid, usually a coconut fatty acid,with trimethylolaminomethane or bis(dihydroxypropyl) amine.

(5) Higher fatty acid partial esters of pentaerythritol ordipentaerythritol.

(6) Monoethers of 1,2-dihydroxycyclohexane produced by the reaction of afatty alcohol with cyclohexene oxide ROH O (7) Products produced by thereaction of glycidol with an active hydrogen containing compound,usually an acid amide, a sulfonamide, or a N-(hydroxyethyl) amide.

It is emphasized that the foregoing discussion is not intended to belimiting as to the scope of this invention with regard to the nonionic,hydroxyl-containing surfactants contemplated by this invention. Rather,it is intended to be illustrative of the wide range of the knownnonionic, hydroxyl-containing, surface active compounds which can beemployed in producing the compounds of this invention.

The olefinically unsaturated sulfones which are employed in producingthe compounds of this invention contain one sulfonyl group (-SO whosevalences are satisfied by bonds to two different carbon atoms, either byway of two monovalent saturated or mono-olefinically unsaturatedhydrocarbon groups, or by a divalent alkenylene hydrocarbon group, thetotal number of carbon atoms in said unsaturated sulfone being from 3 toabout 14, wherein the olefinic double bonds are activated by proximityto the sulfonyl group. In general, suitable unsaturated sulfones arethose having a double bond that is 01,,8 or [3, to the sulfonyl group.Although We do not wish to be bound by theories, it is believed that,for the reaction of the hydroxyl-containing surfactant with theunsaturated sulfone to occur, there must be a conjugated double bondsystem; and that the reactive species is a compound having a double bond(1,5 to the sulfonyl group. However, it has been found that a sulfonehaving a double bond 8, to the sulfonyl group, when heated in basicmedium, will isomerize to form the a,,8- unsaturated sulfone. Regardlessof theory, however, ot,fland ,6,'yunsaturated sulfones are suitable foruse in producing the compounds of this invention. These sulfones arerepresented by the formula:

wherein G, when taken alone, is a monovalent alkenyl group containingfrom 2 to 10, preferably 2 to 4 carbon atoms, such as vinyl, allyl,propenyl, 1,2-octenyl, and the like; G when taken alone, is either analkyl group having from 1 to 10, preferably 2 to 4, carbon atoms or analkenyl group having from 2 to 10, preferably 2 to 4, carbon atoms; andG and G when taken together, form a divalent alkenylene group of from 3to about 14 carbon atoms which when taken with the sulfonyl group formsa heterocyclic ring having from 4 to 7 ring members, and wherein theolefinic double bond is ot,/3- or 5,0;- to the sulfonyl group.

8 Subgeneric to the compounds of the Formula VII are the cylic sulfonesof the formula wherein R is a divalent alkenylene group containing from3 to about 14 carbon atoms which, when taken with the sulfonyl group,forms a heterocyclic ring having from 4 to 7 ring members; each R whentaken individually, is hydrogen or alkyl of from 1 to 4 carbon atoms; Ris a divalent alkylidene group, i.e., a methylene group or analkyl-substituted methylene group containing from 1 to 5 carbon atoms; xis an integer having a value of 0 or 1; and R is an alkyl group or analkenyl group of from 1 to about 10 carbon atoms, preferably from 1 to 4carbon atoms.

As examples of the cyclic sulfones of Formula VIII one can mentionthietene-1,l-dioxide, Z-methylthietene- 1,1-dioxide,S-methylthietene-l,l-dioxide, 4-methylthietene-1,l-dioxide,2,3-dimethylthietene-1,l-dioxide, 2,4- dimethylthietene- 1 1 -dioxide,2,3 ,4-trimethylthietene-l,1- dioxide, 4-ethylthietene-1, 1-dioxide,4-propylthietene-1,1- dioxide, 4-butylthietene-1,l-dioxide,2,3,4-tributylthietene- 1,1 -dioxide, 2,5-dihydrothiophene-l,l-dioxide,2,3-dihydrothiophene-1,1-dioxide, 2-methyl-2,5 -dihydrothiophene-1,1-dioxide, 3-methyl-2,S-dihydrothiophene 1,1 dioxide,3,4-dimethyl-2,S-dihydrothiophene-1,1-dioxide, 3-ethyl-2,S-dihydrothiophene-l,l-dioxide, 3-propyl2,5-dihydrothiophene-1,1-dioxide, 3 -butyl-2,5 -dihydrothiophene-1 1-dioxide, 3,4-dihydro-2H-thiapyran-1,l-dioxide, 3,6 -dihydro-2H-thiapyran-1,1-dioxide, 2,3 dihydro-4H-thiapyran-1,1- dioxide,2-methyl-3,4-dihydrothiapyran-l,l-dioxide, 6-methyl-3,4-dihydrothiapyran-1, l-dioxide, 5,6 dimethyl-3,4-dihydrothiapyran-l,l-dioxide, 2methyl-3,6-dihydrothiapyran-1,1-dioxi-de,4-methyl-3,6-dihydrothiapyran-1,1- dioxide,2,3,4,S-tetrahydrothiapane-1, l-dioxide, 2,3,4,7-tetrahydrothiapane-l,l-dioxide and the like.

As examples of acyclic sulfones of the Formula IX one can mentiondivinyl sulfone, vinyl methyl sulfone, vinyl ethyl sulfone, vinyl propylsulfone, vinyl butyl sulfone, vinyl undecyl sulfone, vinyl dodecylsulfone, diallyl sulfone, allyl methyl sulfone, allyl ethyl sulfone,allyl undecyl sulfone, propenyl methyl sulfone, propenyl ethyl sulfone,propenyl undecyl sulfone and the like.

It should be noted that 2,5-dihydrothiophene-1,l-dioxide and its isomer,2,3-dihydrothiophene-1,l-dioxide, exist in an equilibrium mixture underthe reaction conditions employed for their condensation with thenonionic hydroxyl-containing surfactant. However, this does not affectthe position of addition of the surfactant residue, which in either caseis on the carbon atom B to the sulfonyl group.

It should be further noted that certain sulfone-containing compoundshave previously been employed as surface active agents. As examples ofthese compounds one can mention the sulfonated tetrahydrothiophyl 1,1sulfones disclosed in US. Patent 2,452,949, the tetrahydrothiophyl- 1,l-dioxide esters of long chain fatty acids disclosed in U.S. Patent2,451,299, the 3-tetrahydrothiophyl-1,1-dioxide laurimide disclosed inUS. Patent 2,743,236, and tort.- octyl-p-hydroxyethyl sulfone. However,the sulfonyl group in these known compounds is employed as thehydrophilic portion of the surface active compound. In the compounds ofthis invention, however, particularly, those produced from nonionicsurfactants having poly(ethyleneoxy) chains as the hydrophilic portionof the surfactant, the hydrophilic properties of the sulfonyl group arenegligible when compared with the balance of the hydrophilic portion ofthe compound. In fact, the fi-hydrocarbylmonosulfone group ishydrophobic in nature, as is evidenced by the reduced cloud points ofthe compounds of this invention as compared with the cloud points of theparent, hydroxyl-containing, surface active compound. The reduction ofcloud point clearly is caused by a decrease in solubility orhydrophilicity resulting from the addition of thep-hydrocarbylmonosulfone group. Unexpectedly and surprisingly, however,the adduct retains the detergency and wetting characteristics of thehydroxyl-containing, surface active compound from which it is derived.Thus, sulfones employed in producing the compounds of this invention areemployed to reduce the solubility of known surface active compounds,while at the same time providing a low-foaming, surface active compoundhaving excellent wetting and detergent characteristics.

The mole ratio of hydroxyl-containing surfactant to unsaturated sulfonein the reaction mixture is not particularly critical. However, becauseof the difficulty of removal of unreacted hydroxyl-containing surfactantfrom the reaction product, it is preferred to employ a molar excess ofunsaturated sulfone, generally from about 2 to about 5 moles of sulfoneper molar equivalent of hydroxyl group on the nonionic surfactant.

As has already been indicated, the reaction is catalyzed by basicsubstances. Examples of suitable basic catalysts include alkali metalhydroxides, such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, rubidium hydroxide, or cesium hydroxide; organic quaternaryammonium bases such as benzylitrimethylammonium hydroxide and the like;alkali metal alkoxides, such as sodium methoxide and the like; or analkali metal, particularly sodium or potassium. The choice of catalystdepends primarily on the desired color of the product. When the alkalimetal hydroxides are employed the product usually is dark in color.Lighter colored products are obtained with organic quaternary ammoniumbases, but the product often has an ammoniacal odor. Still lighterproducts are obtained when sodium metal or potassium metal is employedas the catalyst. The catalytic amount of base employed is not narrowlycritical. However, it has been found that from about 0.01 to about 0.5or more molar equivalent of base per molar equivalent of nonionicsurfactant hydroxyl group provides reasonable reaction rates.

The reaction is normally conducted at temperatures of from about 50 C.to about 90 C., with temperatures of from about 65 C. to about 75 C.being preferred. The lower reaction temperature is not particularlycritical, and temperatures of less than 50 C. can be employed ifdesired. However, the reaction rate is too low at these temperatures forreasonable production rates. The maximum specified temperature of 90 0,like the lower temperature limit, is not narrowly critical, and highertemperatures can be employed if desired, depending upon the particularunsaturated sulfone employed in the reaction. The unsaturated sulfones,particularly 2,5-dihydrothiophene-l,l-dioxide and its alkyl-substitutedderivatives are unstable at elevated temperatures, decomposing to formsulfur dioxide and a conjugated diolefin. Although the decomposition mayoccur at various temperatures (see for example, D. Craig, JACS, 65, 1006(1943)), all of the sulfones are quite stable at reaction temperaturesof about 90 C. or less and there is little chance of loss of sulfone dueto decomposition at these temperatures.

The reaction time is not critical and will vary widely depending uponthe reaction temperature and the amount of sulfone employed in thereaction. In general, reaction times of at least 6 hours and often of upto about 24 hours or more are required to achieve suitable conversionsof hydroxyl-containing surfactant to the sulfonyl ethers of thisinvention.

The reaction is preferably conducted under an inert, e.g., nitrogen,atmosphere because in many cases, the presence of oxygen tends to causea discolored product.

Solvents or diluents are unnecessary because excess sulfone provides asuitable reaction medium. However, inert liquid organic compounds suchas ethers, dioxanes, aromatic hydrocarbons,tetrahydrothiophene-l,l-dioxide and the like can be employed if desired.

The compounds of this invention are readily recovered by proceduresknown to the art. When the sulfone employed as a reactant is unstable atelevated temperatures, it can be removed by heating the reaction productat elevated temperatures and removing the sulfur dioxide and dieneproduced by the decomposition. In some cases the hydroxyl-containingnonionic surfactant employed as a reactant can be removed by asalting-out technique wherein calcium chloride is admixed with thereaction product to form an insoluble complex with thehydroxyl-containing compound. This complex precipitates out of thereaction mixture and can be removed by conventional separationprocedures, such as filtration, decantation and the like.

A preferred procedure for producing the compounds of this invention whenthe nonionic, hydroxyl-containing surfactants of Formula VI above, areemployed, particularly those having poly(alkyleneoxy) chains having atleast 4 alkyleneoxy groups in the poly(alkyleneoxy) chains, comprisesadding the selected unsaturated sulfone directly to the mixture from thereaction of the activehydroge-n-containing hydrophobe with ethyleneoxide. This reaction is often a base-catalyzed reaction, and thecatalyst for the reaction of the ethylene oxide and the hydrophobe canbe employed to catalyze the reaction of the hydroxyl group with thesulfone.

The reaction product, even after use of recovery procedures such asthose outlined above, normally contains some unreactedhydroxyl-containing surfactant because, even at high concentrations ofunsaturated sulfone in the reaction mixture, it is ditficult to obtaincomplete reaction with the hydroxyl groups, and as alluded to above, theremoval of the unreacted hydroxyl-containing compound from the reactionproduct is very difficult. However, products containing amounts ofunreacted hydroxyl-containing surfactant as high as 40 mole percent ormore, based on total product, as determined by analysis for hydroxylgroup, still have greatly reduced foaming tendencies and cloud pointswhen compared with the surfactant from which they derived, and areeminently suited for use as detergents, wetting agents and the like.Thus, the compositions of this invention can be more broadly defined, asbeing compositions consisting of the residue of a nonionic,hydroxylcontaining, surface active compound containing n hydroxyl groupsbonded through at least 0.6 n oxygen atoms at the site of said hydroxylgroups to a 5- hydrocarbylmonosulfone group. Compositions containing atleast percent of reacted hydroxyl group are me ferred, with compositionhaving percent or more reacted hydroxyl group being most preferred. Asis apparent, this definition does not refer to a specific compound,rather, it refers to an admixture of compounds in terms of a theoreticalcompound representing the average composition of the admixture. Theformula for this theoretical compound is:

wherein M is a residue of an organic hydroxyl-containing, surface activecompound containing p hydroxyl groups; p is an integer having a value ofat least 1, usually from 1 to 6 and preferably from 1 to about 4; J is afl-hydrocarbylmonosulfone group as defined above; and q is a numberhaving a value of greater than 0 but not greater than 2, and preferablyhas a value of from about 0.6p to p, preferably 0.75p to p, and mostpreferably from 0.9p to p.

The following examples are illustrative. The tests employed to evaluatethe products of the examples are as follows:

(1) Ross-Miles foam test.Determined according to ASTM D-1l7 3-53,employing a concentration of 0.2 weight percent of surfactant indistilled water at a temperature of 50 C. Reported as the foam height incenti- 1 1 meters immediately after agitation and after standing forminutes.

(2) Surface tensiom-Determined according to ASTM D-1331-54T, employing aDu Nuoy tensiometer and a concentration of 0.05 weight percentsurfactant in distilled water at 25 C. Reported in dynes/centimeter.

(3) Relative detcrgcncy.-Deterrnined with a Tergo- Tometer according tothe procedure of J. C. Harris, Detergency Evaluation and Testing, p. 98,Interscience Publishers, Inc., 1954. Four 6 X 6 inch standard soiledswatches supplied by U.S. Testing Company were washed for minutes at 120F., and 120 cycles per minute, employing a solution of 0.2 weightpercent surfactant in distilled water. After hand wringing,power-rinsing for 5 minutes in distilled water and drying by ironing,the reflectance of each swatch was determined with a Model 610 PhotovoltReflection Meter equipped with a green tristimulus filter and a wideangle scanner. The refiectometer was calibrated at 100 using severalthicknesses of white bond paper. Relative detergency was calculated bydividing the reflectance obtained from the surfactantwashed swatches byreflectance obtained from a swatch washed with a solution containing 0.2weight percent Ivory flakes in water and is reported in percent.

(4) Draves wetting test.-Determined at 25 C. according to the proceduredescribed in the 1960 Technical Manual of the American Association ofTextile Chemists and Colorists, vol. 36, p. 160, employing 5-gramstandard skeins supplied by Test Fabrics Inc. Reported as theconcentration in grams of detergent/liter of distilled water requiredfor a wetting time of 20 seconds.

(5) Cloud .p01'nt.Determined from a 0.5 weight percent solution ofsurfactant in distilled water, and is the temperature at which thesolution, on raising the temperature, becomes milky or hazy.

Example 1 A mixture containing 600 grams (1.18 moles) of anonylphenol-ethylene oxide adduct containing an average of 9 ethyleneoxygroups in a poly (ethyleneoxy) chain, 236 grams (2.0 moles) of2,5-dihydrothiophene-1,l-dioxide and 10 grams (0.185 mole) of sodiummethoxide was heated at 68 C., with stirring and under a nitrogenatmosphere, for 5.5 hours At this time 7 grams of 85 percent phosphoricacid was added and the mixture was heated at 68 C. for 1 hour toneutralize the catalyst. The reaction mixture was then heated at 115 C.for 6 hours at 1 mm. mercury pressure to decompose the unreacted2,5-dihydrothiophene-1,1-dioxide. After cooling the reaction mixture toroom temperature and filtering there was recovered 590 grams of productwhich contained 66.5 weight percent of the 3-[nonylphenoxypo1y(ethyleneoxy)1tetrahydrothiophene 1,1 dioxide, 16.5 weight percentunreacted nonylphenol-ethylene Oxide adduct and 17 weight percentunreacted dihydrothiophene- 1,1-dioxide. The properties of this productas determined by the above-described tests are tabulated below, togetherwith the results of equivalent tests conducted on samples of thenonylphenolethylene oxide adduct employed in producing the product ofthis invention.

Foam Height, mm. Surface Relative Wetting Cloud Tension, Detergency,Test, Point, dynes/em. Percent gm./l. C. Ini- Alter tial 5 min.

Product 1 80 3 31. 5 1 114 0. 68 42. 2 Control.-- 1 160 50 29.2 116 0.6855.8

1 Measured at 40 C. because of reduced cloud point.

From the foregoing table it is readily apparent that the compositions ofthis invention have greatly reduced foaming tendencies and cloud pointswhen compared with the parent hydroxyl-containing surfactant, without asignificant change in Wetting or detergency properties, even 12 atconcentrations of the sultone-containing surfactant of this invention inthe detergent composition as low as 66 weight percent.

Example 2 A mixture of 495 grams (0.75 mole) of a nonylphenolethyleneoxide adduct containing an average of 10.5 ethyleneoxy groups inapoly(ethyleneoxy) chain, and 1 gram (0.0435 gram atom) of metallicsodium was heated at 100 C., with stirring under a nitrogen atmospherefor 3 hours. The reaction mixture was cooled to C. and 266 grams (2.25moles) of 2,5-dihydrothi0phene-1,l-dioxide was added. The resultingmixture was maintained at 55 to 70 C. for 24 hours, after which time itwas cooled to room temperature, admixed with 2.5 liters of ethyl etherand filtered. The filtrate was flash distilled to remove the ethyl etherand vacuum dried to recover 640 grams of product.

A ZOO-gram sample of the product was heated at 120 C, for 2.5 days at0.1 mm. pressure to decompose unreacted2,5-dihydrothiophene-1,l-dioxide. There was recovered 179 grams of aproduct containing 74.4 weight percent 3- [nonylphenoxypoly(ethyleneoxy)tetrahydrothiophene-l, l-dioxide, 10.4 weight percent unreactednonylphenolethylene oxide adduct, and 15.2 weight percent unreacteddihydrothiophene-1,1-di0xide.

The properties of this product and of the nonylphenolethylene oxideadduct are tabulated below.

Foam Height, mm. Surface Relative Wetting Cloud Tension, Detergeney,Test, Point, dynes/em. Percent gmJl. C. Ini- After tial 5 min.

Product. 1 10 31. 5 1 114 0. 55 49. 0 Control.-- 1 190 10 29.8 112 0 7063.5

1 Measured at 45 0. because of reduced cloud point.

Example 3 Foam Height, mm. Surface Relative Wetting Cloud Tension,Detergeney, Test, Point, dynes/cin. Percent grnJl. 0. Im- After tial 5min.

Product. 60 10 30.7 107 47. 0 Control." 190 10 29. 8 112 63. 5

Example 4 Employing procedures similar to those described in Example 2,300 grams (0.38 mole) of a nonylphenol-ethylene oxide adduct containingan average of 13 ethyleneoxy groups in a poly(ethyleneoxy) chain, grams(0.76 mole) of 2,5-dihydrothiophene-1,l dioxide, and 2 grams (0.087 gramatom) of sodium was heated at 65 to 70 C. for 6 hours. There wasrecovered 311 grams of crude product containing 76 weight percent3-[nonylphenoxypoly (ethyleneoxy) ]tetrahydrothiophene-1 1 -dioxide.

The product was admixed with toluene and with solid calcium chloride.The solids were filtered from the mix- Foam Height, mm.

Relative Cloud Detergency, Point, Initial After Percent C.

min.

Product:

Pure 135 5 116 60 Crude 195 5 108 74 Control a 220 a. 91 93 From theforegoing table it is clear that the product of this example,particularly when at a purity of 97 percent, has outstanding utility asa low temperature laundry detergent.

Example 5 Employing procedures similar to those described in Example 2,436 grams (0.164 mole) of the adduct of (a) the reaction product ofbutanol, ethylene oxide and propylene oxide, the mole ratio of ethyleneoxide to propylene oxide being 1/9, said reaction product having amolecular weight of about 1500, and (b) ethylene oxide, said adducthaving an average of 34 ethyleneoxy groups in a poly(ethyleneoxy) chain,1 gram (0.0435 gram atom) of sodium and 58 grams (0.492 mole) of2,5-dihydrothiophene-1,1-dioxide was heated at 65 C. for 24 hours. Therewas recovered 435 grams of product which contained 82.9 weight percentsulfone adduct, 10.2 weight percent unreacted butoxy[poly(ethyleneoxy)-poly(propyleneoxy)]poly(ethyleneoxy) adduct, and 6.9weight percent unreacted dihydrothiophene-l,l-dioxide,

The properties of this product and of the butoxy[poly (ethyleneoxy)poly(propyleneoxy) poly(ethyleneoxy) adduct are tabulated below.

Foam Height, mm. Surface Relative Wetting Cloud Tension, Detergency,Test, Point, dynes/cm. Percent gm./l. C. Ini- After tial 5 min.

Product 130 35 39.0 96 3.15 93.4 Control 145 37.4 106 3. 9 100 Althoughthe relative detergency of the product of this example was lower thanthat of the parent hydroxyl-containing surfactant, it is readilyimproved by rebalancing of the hydrophobe-hydrophile ratio by methodsknown to those skilled in the art.

Example 6 The properties of this product and of the tridecanolethyleneoxide adduct are tabulated below.

Foam Height,

mm. Surface Relative Cloud Tension, Detergency, Point, dynes/cm.Percent; 0. Initial After 5 min.

Product 190 4 28. 1 74. 6 Control 225 10 29. 4 98 90. 0

Example 7 Employing apparatus and procedures similar to those describedin Example 1, a mixture containing 448 grams (0.52 mole) of a dodecylmercaptan-ethylene oxide adduct containing an average of 15 ethyleneoxyunits in a poly-(ethyleneoxy) chain, 307 grams (2.60 moles) of 2,5-dihydrothiophene-1,1-dioxide and 10 grams (0.185 mole) of sodiummethoxide was heated at 65 to 70 C. for 12 hours. There was recovered398 grams of product containing 81.05 percent3-[dodecylthiopoly(ethyleneoxy)] tetrahydrothiophene-1,1-dioxide, 16.4percent unreacted dodecyl mercaptan-ethylene oxide adduct, and 2.55%unreacted dihydrothiophene-l,l-dioxide.

The properties of this product and of the dodecyl mercaptan-ethyleneoxide adduct are tabulated below.

Employing procedures similar to those described in Example 2, a mixtureof 465 grams (0.75 mole) of a trimethylnonylphenol-ethylene oxide adductcontaining an average of 10 ethyleneoxy units in a poly(ethyleneoxy)chain, 442 grams (3.75 moles) of 2,5-dihydrothiophene- 1,1-dioxide, and1.5 grams (0.038 gram atom) of potassium was heated at 65 to 70 C. for21 hours. There was recovered 429 grams of crude product containing 88.1percent 3- [trimethylnonylphenoxypoly(ethyleneoxy)]tetrahydrothiophene-l,l-dioxide and 11.9 percent unreactedtrimethylnonylphenol-ethylene oxide adduct.

A portion of this crude product was admixed with toluene and thenslurried with solid calcium chloride and filtered to remove unreactedtrimethylnonylphenol-ethylene oxide adduct. The process was repeated 3additional times and the toluene was evaporated from the product whichcontained 94.4 percent 3-tetrahydrothiophyl-1,1- dioxide adduct and 5.6percent unreacted trimethylnonylphenol-ethylene oxide adduct.

The properties of the pure and crude products and of thetrimethylnonylphenol-ethylene oxide adduct are tabulated below.

Foam Height, mm.

Relative Cloud Detergency, Point, Initial After Percent C.

5 min.

Product:

1 5 Example 9 Employing procedures similar to those described in'Example 1, a nonylphenol-ethylene oxide adduct is reacted with3-methyl-2,S-dihydrothiophene-1,1edioxide to produce a product havingreduced cloud point and foaming tendency.

Example 10 Employing procedures similarto those described in Example 1,a 'nonylphenol-ethylene oxide adduct is .re-

acted'with 3-cthoXy-2,5-dihydrothiophened,l-dioxide to produce a producthaving reduced cloud point and foamin g tendency.

I Example 11 ing tendency.

Example 12 Employing procedures similar to'those described in Example 1,1a

' acted With ,divinyl sulione to produce a product having reduced cloudpoint and foaming'tendency.

What is claimed is:

1. A non-ionic surface active compound of the formula:

nonylplienol-ethylene oxide adduct is re I Bl vR s where Y is an alkylphenoxy radical said alkyl having from 4-22 carbon atoms, X is ahydrophilic alkyleneoxy chain containing individually one or morealkyleneoxy members selected from the group consisting of methyleneoxy,ethyleneoxy, propyleneoxy and butyleneoxy and mixtures of saidethyleneoxy, methyleneoxy and propyleneoxy members where the atomicratio of carbon to oxygen is from about 1.5:1 to about 21:1, in saidmixture, X may be a hydrophilic styreneoxy moiety containing one or morestyreneoxy repeating units, R is a member selected from the groupconsisting of hydrogen or 1-4 carbon atom alkyl radical and y a lowercase may vary from 1 to 6.

2. The compound of claim 1 where y=1.

' oxy, ethyleneoxy,

16 3. A non-ionic surface active composition of matter of the formula:

where Y is an alkyl phenoxy radical, said alkyl having from 4-22 carbonatoms,)( is a hydrophilic alkyleneoxy. I

chain containing individually one or'more alkyleneoxy members selectedfrom the group consisting of methylenepropyleneoxy and butyleneoxy andmixtures of said ethyleneoxy, metlryleneoxy and propyleneoxy memberswhere the atomic ratio of carbon to oxygen isfrom about 1.5 :lto about2.1: 1, in said mixture,

' X'm'ay be a hydrophilic styreneoxy' moiety containing one or morestyreneoxy repeating units,:R is a memberselected from the groupconsisting of hydrogen or 1-4 carbon atomsalkyl radical, y may vaiy from1 to 4 and n has a value of at least 0.6y.

4. The composition of claim 3 wherenhas a value of at least 0.75; I

5. The composition of claim '3 Where said hydrophilic alkyleneoxy chainis' a poly(ethyleneoxy) chain.

' 6. 3 -.[nonylphenoxypoly(ethyleneoxy)]tetrahydrothio phone-1,1-dioxidew'he'resaid polyethyleneoxyrnoiety.is'

hydrophylic.

7. 3 [nonylphenoxypoly(ethyleneoxy) ltetrahydrothiophone-1,1-dioxidewhere said polyethyleneoxy moiety cornprise an average of about 9 to10.5 ethyleneoxyrnoieties.

' 8. 3 '[trimethylnonylphenoxypoly(ethyleneoxy)]tetra-'hydrothiophene-1,1-dioxide, where said poly(ethyleneoxy) moiety ishydrophilicr 9. 3 [trimethylnonylphenoxypoly(ethy1eneoxy)]tetrahydroth-iophene-1,1-dioxide,' said poly (ethyleneoxy)moiety being hydrophilic and comprises an average of about 10ethyleneoxy moieties.

References Cited UNITED STATES PATENTS 2,419,082 4/1947 Morris et al.260-332.1 2,482,631 9/1949 Morris et a]. 260-3321 2,492,927 12/1949Ballard et a1. 260-332.1 2,882,278 4/1959 McConnell et al. 260-332.l3,098,793 7/1963 Loev 260332.1

FOREIGN PATENTS 682,157 11/1952 Great Britain.

WALTER A. MODANCE, Primary Examiner.

JAMES A. PATTEN, Assistant Examiner.

1. A NON-IONIC SURFACE ACTIVE COMPUND OF THE FORMULA: